JPH03237131A - End modified polyether amide resin - Google Patents

Abstract

PURPOSE:To obtain the title resin useful for packaging foods, suppressing evolution of low-molecular bad-smelling substances or low-molecular compounds during melt polymerization and molding, comprising specific constituent units, containing a specific polyether amide at the ends in a given ratio. CONSTITUTION:The objective resin comprising a polyether amide which is composed of constituent units shown by formula I to formula IV (R<1> to R<3> are 2-4C alkylene; R<4> to R<6> are 2-36C aliphatic or aromatic hydrocarbon; n is 0-180; m is 1-400), has 10,000-100,000 molecular weight and contains 1-22C hydrocarbon group at the ends in which the number of the hydrocarbon groups is 5-100% based on the whole end groups of the polyether amide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to terminally modified polyetheramide resins. Specifically, the present invention relates to a polyetheramide resin which has a reduced amount of easily extracted low molecular weight compounds, generates less low molecular weight compounds after molding (after heat history), and has good thermal stability.

[Conventional technology and issues]

Polyetheramide resin has antistatic properties, heat resistant moldability,
It has excellent mechanical strength and is used for various purposes (for example, Japanese Patent Publication No. 45-7559), but recently its use in the food packaging field, especially in food packaging films and sheets, has been considered due to its flexibility and mechanical strength. There is.

However, polyetheramide resins have been avoided in food-related fields because they produce low-molecular-weight odorous substances and low-molecular compounds such as polyamide oligomers during their melt polymerization. Moreover, even if the low-molecular-weight compound is once removed using an appropriate solvent, it will be generated again when melt-molding is performed, which is not desirable in terms of thermal stability.Therefore, further improvements have been desired.

[Means to solve the problem]

The present inventors have conducted intensive research to solve the above problem, and have found that the a[) group and the carboxy group at the end of the polymer molecule, which polyether amide resin inevitably has, can be used for low-molecular-weight odorous substances and other low-molecular-weight substances. It was found that this compound is involved in the generation of compounds. The present invention was completed based on the knowledge that by sealing these amino groups and carboxy groups with specific hydrocarbon groups, the generation of the above-mentioned low-molecular compounds, etc. can be greatly suppressed.

That is, the purpose of the present invention is to provide a polyetheramide resin having great industrial value, and the gist thereof is the following structural formula (1), ([], (1) or [IV] It is a polyether amide having a molecular weight of 10,000 to 10,000 and having a hydrocarbon group having 1 to 22 carbon atoms at the terminal, and the number of the hydrocarbon groups is equal to the total number of terminals of the polyether amide. A terminal-modified polyetheramide resin having 5 to 100% of the number of groups.

(However, R'+R"+R3 is a linear or branched alkylene group having 2 to 4 carbon atoms, and R4, Rs, and R6 are straight chain or branched alkylene groups having 2 to 4 carbon atoms.
36 aliphatic, cycloaliphatic or aromatic hydrocarbon groups;
n is 0 to 180. m is 1-400. ).

The present invention will be explained in detail below.

The terminal-modified polyetheramide resin of the present invention has the following general formula (1) in which polyether units and polyamide units are connected.
), (II), (III) or [IV] as the main structural unit.

Poly(ether amide) can be easily obtained by, for example, forming an amide bond between a polyether having an amino group or a carboxyl group at the end and a polyamide having a carboxyl group or an amino group at the end through a condensation reaction.

Each of these structural units represented by CI) to [IV] forms the polyether amide of the present invention by itself, but in some cases, the polyether amide of the present invention may be a copolymer containing two or more of these. There may be.

R representing an alkylene group in the above general formulas (I) to (mV)
I, R and R3 are linear or branched alkylene groups having 2 to 4 carbon atoms, such as ethyl group, propyl group, isopropyl group, and tetramethylene group;
It is. In addition, the integer n is θ~180, preferably 0~6
It is about 0.

In the above general formula, R4 has 2 to 36 carbon atoms, preferably 2 to 36 carbon atoms.
25, more preferably 2 to 11 aliphatic, alicyclic or aromatic hydrocarbon groups, and are residues of lactams or aminocarboxylic acids used in the production of polyamides, which will be described later. R5
is an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 36 carbon atoms, preferably 2 to 22 carbon atoms, more preferably 2 to 7 carbon atoms, and is a residue of a diamine described below. R6 has 2 to 3 carbon atoms
6, preferably 2 to 24, more preferably 2 to 11 aliphatic, alicyclic, or aromatic hydrocarbon groups, and is a residue of a dicarboxylic acid described below. In addition, the integer m is 1 to 400,
Preferably it is 1-120.

The content of polyether units in the poly(ether amide) of the present invention at the bottom of the tank is 5 to 75% by weight, preferably 10% by weight.
~50% by weight is suitable from the viewpoint of a balance between mechanical strength and flexibility.

The terminal-modified polyetheramide resin of the present invention is obtained by introducing a certain proportion of hydrocarbon groups into the terminals of polyetheramide consisting of poly(etheramide) units to modify the terminals.

The hydrocarbon group (terminal hydrocarbon group) that the terminal-modified polyetheramide resin of the present invention has at the end has 1 to 1 carbon atoms.
22, specifically methyl group, ethyl, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Aliphatic hydrocarbon groups such as tetradecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, octadecyl group, eicosyl group, tocosyl group, alicyclic group such as cyclohexyl group, methylcyclohexyl group, cyclohexylmethyl group Examples include aromatic hydrocarbon groups such as a phenyl group, tolyl group, benzyl group, and β-phenylethyl group.

These terminal hydrocarbon groups are introduced by using a monocarboxylic acid and/or a monoamine, which will be described later, during the production of polyether amide.

In addition to the above-mentioned terminal hydrocarbon groups, the terminal groups of the modified polyetheramide resin of the present invention include amino groups and/or carboxyl groups derived from the raw materials for producing polyetheramide, which will be described later. is the sum of the numbers of the above terminal hydrocarbon groups, amino groups and/or carboxyl groups. In the present invention, the number of the terminal hydrocarbon groups is 5 to 100% of the total number of terminal groups. If this number is small, the generation of reducing impurities during melt polymerization and melt molding cannot be suppressed, so it is set to 5% or more, preferably 10% or more. Furthermore, if the number of terminal hydrocarbon groups is close to 100% of the total number of terminal groups, production will not be easy, so from an industrial perspective, it is preferably 95% or less, more preferably 90% or less.

The number of carbon atoms in the terminal hydrocarbon group of the polyetheramide resin of the present invention is 1 to 22, preferably 6 to 22, and more preferably 12 to 22.

Examples of the terminal hydrocarbon group include the above-mentioned aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, among which aliphatic hydrocarbon groups, preferably linear ones, Furthermore, a long chain alkyl group having 12 to 22 carbon atoms,
It is preferable because there is little scattering during vacuum polymerization and molecular weight control is easy.

The terminal-modified polyetheramide resin of the present invention has a molecular weight (
Mn) is io, ooo to too, ooo, preferably 15,000 to so, ooo.

The molecular weight was determined by the following formula, with the total number of terminal groups being the sum of the amount of terminal groups that can be analyzed (amino groups and carboxyl groups) (μeq/g) and the amount of terminal modifier (described later) (μeq/g) used. It is a value.

Next, a method for producing the terminal-modified polyetheramide resin of the present invention will be explained.

Poly(ether amide) can be easily obtained by, for example, forming an amide bond between a polyether having an agono group or a carboxyl group at the end and a polyamide having a carboxyl group or an amino group at the end through a condensation reaction.

Polyethers having amino groups or carboxyl groups at the terminals can be prepared by ring-opening polymerization of alkylene oxides such as ethylene oxide, propylene oxide, etc. or tetrahydrofuran. It can be easily obtained by substituting the terminal hydroxyl group with an amino group and/or a carboxyl group.

Examples of the above-mentioned amino group substitution method include direct amination of the hydroxyl group or cyanoethylation followed by reductive amination, and carboxyl group substitution includes oxidative carbonylation.

In the present invention, polyether (5) having amino groups at both ends or polyether ('b) having carboxyl groups at both ends is preferably used as the raw material polyether.

HlN-R'0→R''0)-R'-NH, (a
lHOOC=R'0→R"0h-R'-COO)I
(R', R", R3 are the same as above) On the other hand, polyamides having carboxyl groups and amino groups at the terminals can be produced by ring-opening polymerization of lactams having 3 or more rings, polycondensation of polymerizable aminocarboxylic acids, or It can be obtained directly by polycondensation of dicarboxylic acids and diamines.

Specifically, the lactam includes ε-caprolactam,
Examples include enantholactam, capryllactam, lauryllactam, α-pyrrolidone, α-piperidone, and the like.

The polymerizable aminocarboxylic acid is preferably ω-
Amanoic acid is mentioned, and ω-ahanoic acid having 2 to 25 carbon atoms is usually used. Specifically, 6-aminocaproic acid, 7-aminohebutanoic acid, 9-aminononanoic acid, 11-
Examples include aminoundecanoic acid.

As the dicarboxylic acid, a dicarboxylic acid having 2 to 36 carbon atoms is usually used, and specific examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, and undecanedioic acid. , dodecanedioic acid, tridecadionic acid, tetradecadionic acid, hexadecadionic acid, hexadecenedioic acid, octadecadionic acid, octadecenedioic acid, eicosandioic acid, eicocenedioic acid, eicosadienedionic acid, tocosandioic acid , 2.2.4-) aliphatic dicarboxylic acids such as limethyladipic acid, cycloaliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, terephthalic acid,
Examples include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, and xylylene dicarboxylic acid.

Furthermore, examples of dicarboxylic acids having 36 carbon atoms include dimerized fatty acids. Dimerized fatty acids are polymerized fatty acids obtained by polymerizing fatty acids, such as saturated, ethylenically unsaturated, acetylenically unsaturated, natural or synthetic basic fatty acids having 8 to 24 carbon atoms.

In addition, as the diamine, diamines having 2 to 24 carbon atoms are usually used, and specifically, ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, etc. Cia-kun, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, hexadecamethylene diamine, octadecamethylene diamine, 2,2.4 (or 2,4゜4 )-Trimethylhexamethylene diamine, aliphatic diamines such as cyclohexane diamine, methylcyclohexane diamine, bis-(4,4'-anocyclohexyl)methane, and xylylene diamine. Examples include aromatic diamines such as Examples of diamines having 36 carbon atoms include dimeric amines obtained by converting the carboxyl groups of dimerized fatty acids into amino groups.

Specific examples of the polyamides mentioned above include nylon 4. 6. 7. 8. 11. 12.6°6
．． 6.9.6.10, 6.11.6.12, 6T, 6/
Examples include 66.6/12.6/6T.

Among the above-mentioned polyamides, polyamides represented by the following formula (C) or (bl) are preferably used for polyamides produced by ring-opening polycondensation of lactams or polycondensation of ω-amino acids.

H-(-N)IR'c)=-NHR"N)It
(d) (R', R', R- are the same as above) The polyamide with carboxyl groups at both ends represented by formula (C) above is obtained by adding the above-mentioned dicarboxylic acid to the basic polyamide obtained by ring-opening polycondensation of lactam. The polyamide having agono groups at both ends represented by the above-mentioned formula 1d) can be obtained by adding the above-mentioned diamine to the same basic polyamide.

On the other hand, polyamides produced by polycondensation of dicarboxylic acids and diamines can be produced directly by using more than the theoretical amount of either raw material.
A polyamide (f) having one or both terminal amino groups can be obtained.

As described above, the poly(ether amide) of the present invention is
The above-mentioned formula (
1), (■), (III) or [IV].

That is, the above formula (1) or (If) is a polyether having amino groups at both ends represented by the general formula (a) and a polyamide having carboxyl groups at both ends represented by the general formula (C1 or (e)). - Formula (II) or [IV] is a repeating structural unit obtained by condensing the above-mentioned general formula (
It is a repeating structural unit obtained by condensing a polyether having carboxyl groups at both ends represented by b) and a polyamide having amino groups at both ends represented by general formula (d) or (f).

The terminal-modified polyetheramide resin of the present invention is obtained by introducing a hydrocarbon group into the terminal of such poly(etheramide) to modify the terminal.

The terminal-modified polyetheramide resin of the present invention is obtained by introducing a certain proportion or more of hydrocarbon groups into the terminals of the poly(etheramide) described above to modify the terminals.

Terminal modification of poly(ether amide) is carried out by reacting the amino group and carboxyl group, which are the terminal groups of poly(ether amide), with a monocarboxylic acid and/or a monoamine as a terminal modifier.

As the monocarboxylic acid, a monocarboxylic acid having about 2 to 23 carbon atoms is usually used, and specific examples include acetic acid, propionic acid, acetic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, and capric acid. acids, aliphatic monocarboxylic acids such as undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ξ ristoleic acid, oleic acid, linoleic acid, cyclohexanecarboxylic acid acid,
Examples include alicyclic monocarboxylic acids such as methylcyclohexanecarboxylic acid, and aromatic monocarboxylic acids such as benzoic acid, toluic acid, ethylbenzoic acid, and phenylacetic acid. Note that corresponding derivatives, such as acid anhydrides, esters, amides, etc., which can play the same role as the above-mentioned acids during the reaction can also be used.

On the other hand, as monoagons, various monoamines having about 1 to 22 carbon atoms are usually used, and specifically, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, Octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine,
Aliphatic monoamines such as tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, eicosylamine, tocosylamine, octadecylamine, fats such as cyclohexylamine, methylcyclohexylamine Examples include cyclic monoamines, benzylamine, and aromatic monoamines such as β-phenylethyl ξ.

Through the above reaction, a hydrocarbon group corresponding to the monocarboxylic acid and/or monoamine used as the hydrocarbon group-introducing agent is introduced into the terminal amino group and/or carboxyl group of the poly(ether amide).

The terminal-modified polyetheramide resin of the present invention can be produced by a known condensation reaction.

First, obtain the desired polyamide from the polyamide raw material,
Next, the above-mentioned polyether whose terminal groups have been appropriately modified is added to this to perform a condensation reaction.The monocarboxylic acid and/or monoamine used for terminal modification starts the reaction under reduced pressure from the start of the above-mentioned condensation reaction. It can be added at any stage up to. Furthermore, when a monocarboxylic acid and a monoamine are used together, they may be added at the same time or separately.

The terminal-modified polyetheramide resin of the present invention can be used in food-related fields, mainly as packaging bodies that require direct contact with foods, specifically films, sheets, blow containers, etc.

In addition, the packaging body referred to in the present invention refers to packaging materials including films, sheets, blow containers, etc. In addition to extrusion molding such as T-die method and inflation method, injection molding, blow molding,
It is molded by subjecting it to a generally known molding method for thermoplastic resins, such as vacuum molding. In addition, other ingredients such as pigments, dyes, heat resistant agents, antioxidants, weathering agents, lubricants, crystal nucleating agents, antistatic agents, plasticizers, other polymers, etc. may be added as long as they do not impair moldability or physical properties. can be added.

Further, when the package made of the terminal-modified polyetheramide resin of the present invention is a film or sheet, it may be used unstretched or after being stretched by a known method.

Further, a known resin may be laminated onto the package by a known method such as a coextrusion method or a lamination method.

〔Example〕

EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the examples, various measured values were obtained by the following methods.

+1) End group analysis The number of hydrocarbon groups was measured by gas chromatography after hydrolyzing the modified polyetheramide resin using hydrochloric acid. Amino groups were measured by dissolving polyamide in phenol and titrating with 0.05 N hydrochloric acid. In addition, carboxyl groups can be obtained by dissolving polyamide in benzyl alcohol. Measured by titration with IN caustic soda.

(2) Relative viscosity; determined at 1% concentration in m-cresol using an Ubbelohde viscosity tube at 30°C>.

(3) Terminal modification rate (4) Measurement of low molecular weight compound amount 10 g of the pellet was extracted with 100 g of demineralized water at 121°C for 20 minutes. After cooling to room temperature, the liquid was passed through a 0.2 μm Teflon filter, and the filtrate was evaporated to dryness. After that, the weight was measured.

(5) Measurement of Odorous Substances 10 g of a sample was placed in a glass tube with a septum, replaced with N, heated at 100° C. for 30 minutes, and 0.5 wj of gas remaining in the head space was sampled with a gastight cylinder and analyzed by GC.

Examples 1 to 6 A 2001 autoclave was charged with the polyamide raw materials listed in Table 1, sealed in an N2 atmosphere, and maintained at a constant pressure (IO
After heating the mixture to 240° C. with stirring and carrying out a reaction under pressure for 2 hours, the polyether and terminal modifier listed in Table 1 were added, and the reaction was further carried out under pressure for 2 hours with stirring. The pressure was gradually released to a predetermined pressure, and the reaction was carried out under reduced pressure for 2 hours.

The stirring was stopped, N8 was introduced to restore the pressure to normal pressure, and the mixture was extracted as a strand and pelletized.

The pellets thus obtained were extracted with hot water at 100°C (
water ratio 3.0.50 min XIO batch extraction) and after drying, 3
．． A test piece was molded using a 6-ounce injection molding machine (manufactured by Toshiba Machine ■) at a resin temperature of 240°C and a mold temperature of 60°C, and easily extractable low molecular weight compounds and odor were measured before and after the acid form. The results are shown in Table 1.

Comparative Example 1.2 The same operations as Examples 1 to 6 were performed except that no terminal modifier was added. The results are shown in Table 1.

〔Effect of the invention〕

The terminal-modified polyether composite resin of the present invention greatly suppresses the generation of low-molecular-weight odorous substances and low-molecular compounds during melt polymerization and molding, and is suitable for heat chambers, especially films and containers for food packaging. be.

Claims (1)

[Claims] (1) The following structural formula [I], [II], [III] or [IV]
Consisting of the structural unit represented by, and having a hydrocarbon group having 1 to 22 carbon atoms at the end and a molecular weight of 10,000 to 100,00
1. A terminal-modified polyetheramide resin in which the number of hydrocarbon groups is 5 to 100% of the total number of terminal groups of the polyetheramide. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・[III] ▲Mathematical formulas , chemical formulas, tables, etc. ▼ ... [IV] (However, R^1, R^2, R^3 are linear or branched alkylene groups having 2 to 4 carbon atoms, R^4, R^5 , R^6 represents an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 36 carbon atoms. n is 0 to 180, and m is 1 to 400.)